JPH1129557A - Pyrimidine derivative, liquid crystal composition containing the same and liquid crystal display element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a component for a liquid crystal composition especially for a thin film transistor type liquid crystal display element, containing a 1,4-phenylene group substituted with a fluorine atom the lateral position and a pyrimidin-2,5-diyl group. SOLUTION: This compound is shown by formula I (R is a 1-20C alkyl or the like; n1 and n2 are each 0-2 and n1+n2 is 1 or 2; ring A and ring B are each a group of formula II or the like, and at least one group is the group of formula II and n1 and/or n2 corresponding to the formula II is 1 or 2; Za to Zc are each a single bond, or the like; Q1 to Q7 are each methyl or the like, and when one or more of Za to Zc are CH2 CH2 , Q2 is F; Y is a halogen or the like) such as 2-[3-(3-fluoro-4-trifluoromethoxyphenyl)-3,5-difluorophenyl]-5- pentylpyrimidine. The compound of formula I is obtained, for example, by a method for reacting a compound of formula III with a compound obtained from a compound of formula IV, lithiating the resultant substance and treating the resulting substance with zinc chloride to give a compound of formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel liquid crystal compound (hereinafter, the term "liquid crystal compound" is a general term for compounds having a liquid crystal phase and useful compounds which do not show a liquid crystal phase but are used as constituents of liquid crystal compositions). ), A liquid crystal compound particularly suitable for use as a component of a liquid crystal composition for a TFT type liquid crystal display element, a liquid crystal composition containing this compound,
And a liquid crystal display device formed using the liquid crystal composition.

[0002]

2. Description of the Related Art A liquid crystal display device utilizes an optical anisotropy and a dielectric anisotropy of a liquid crystal material. Depending on the display method, a TN (twisted nematic) mode, a DS
There are display methods such as (dynamic scattering) mode, GH (guest / host), DAP (orientation phase change) mode, and STN (super twisted nematic) mode. In recent years, in order to meet the demand for higher display quality, the demand for an active matrix type display element represented by a thin film transistor (TFT) is increasing. The performance required of the liquid crystal material is different for each display method, but the liquid crystal material used in any display element must be stable to moisture, air, heat, light, etc., and should be as wide as possible around room temperature. Shows a liquid crystal phase in a temperature range, has low viscosity, has good compatibility with other liquid crystal compounds, and has a large dielectric anisotropy value (Δ
ε), have an optimum refractive index anisotropy value (Δn), and be chemically and electrically stable. In particular, a high voltage holding ratio is required for an active matrix type display element. However, at present, no single compound satisfies all of these conditions, and at present, a liquid crystal composition obtained by mixing several types of liquid crystal compounds or liquid crystal compounds is used.

Recently, in a TFT type liquid crystal display device,
There is a demand for a low-voltage drive and a high response speed. Therefore, liquid crystal materials exhibiting a high voltage holding ratio and having a large Δn and a large Δε are being actively developed. It has been known that a fluorine-substituted liquid crystal material shows a high voltage holding ratio and that a liquid crystal compound containing a plurality of aromatic rings has a large Δn. It is also known that compounds in which the aromatic ring is a pyrimidine ring have a large Δε. Based on such knowledge, it is expected that a fluorine-substituted liquid crystalline compound having a pyrimidine ring has both a large Δn and a large Δε and a high voltage holding ratio. JP-A-2-233626 discloses a fluorine-substituted liquid crystal compound (compound (10)) having a pyrimidine ring.

[0004]

Embedded image

The voltage holding ratio of the compound (10) synthesized and measured by the present inventors according to the description in JP-A-2-233626 is 97.5% at 25 ° C. and 92.9% at 100 ° C.
Met. The physical properties of the compound (10) calculated by the extrapolation method from the respective physical properties and the mixing ratio of the composition obtained by dissolving the compound (10) in the mother liquid crystal having a nematic phase and the mother liquid crystal are as follows: NI transition point is 83.7 ° C, Δε
Was 18.7 and Δn was 0.204. Although this has a relatively high voltage holding ratio, the value of Δε is insufficient to meet the demand for low-voltage driving of the liquid crystal display device. In addition, as will be described later in the section of the comparative example, the compound (10) has a disadvantage that the low-temperature compatibility with other liquid crystal compounds is poor. Liquid crystal materials with poor low-temperature compatibility cannot increase the mixing ratio in the liquid crystal composition,
Even if it has other excellent characteristics, it cannot contribute to the improvement of the characteristics of the liquid crystal composition.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal compound having a high voltage holding ratio, a large Δn and a large Δε, and having excellent low-temperature compatibility with other liquid crystal compounds. It is another object of the present invention to provide a liquid crystal composition containing the same, and a liquid crystal display device formed using the same.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a 1,4-phenylene group having at least one fluorine atom substituted at the lateral position and pyrimidine-2. The present inventors have found that the compound represented by the general formula (1) having a 5,5-diyl group is a liquid crystal compound having expected performance, and have completed the present invention. That is, the present invention is as follows. (1) General formula (1)

[0008]

Embedded image

(Wherein R represents a hydrogen atom or a group having 1 to 1 carbon atoms)
20 represents an alkyl group, wherein one or more hydrogen atoms in the alkyl group may be substituted with a halogen atom;
One or more —CH ₂ — in the group is an oxygen atom or —CH ₂ ＝
CH ₂ — may be substituted, but no oxygen atom is adjacent; n 1 and n 2 are each independently 0,
And the sum of n1 and n2 is 1 or 2, and ring A and ring B are each independently 1,4-phenylene, a fluorine-substituted 1,4 represented by the formula (a). -Phenylene or 1,4-cyclohexylene, but a ring A
And at least one of the ring B is a fluorine-substituted 1,4-phenylene represented by the formula (a), and n1 and / or n2 corresponding to the fluorine-substituted 1,4-phenylene are 1 or 2; In 1,4-cyclohexylene, one or more non-adjacent —CH ₂ — in the group may be substituted with an oxygen atom, and 1,4-cyclohexylene has one or more hydrogen atoms in the group being halogen. may be substituted with atoms; Za, Zb, and Zc are independently a single bond, _{respectively, -CH 2 CH 2 -, -} COO -, - CF 2 O- or -CH ₂ CH ₂ CH ₂ CH ₂ - indicates; Q _1, Q _2, Q
₃ , Q ₄ , Q ₅ , Q ₆ and Q ₇ each independently represent a hydrogen atom, a halogen atom or a methyl group;
When at least one of Zb and Zc is —CH ₂ CH ₂ —, Q ₂ is a fluorine atom; Y represents a hydrogen atom, a halogen atom, or a halogenated alkyl group having 1 to 5 carbon atoms. One or more non-adjacent methylene groups in the alkylated alkyl group may be substituted with an oxygen atom or a sulfur atom; and each element constituting the compound may be substituted with its isotope. A) a pyrimidine derivative represented by the formula:

(2) In the general formula (1), n1 is 0
And n2 is 1, Za, Zb and Zc are all single bonds, Q ₁ and Q ₃ are both hydrogen atoms, Q ₂
Is a fluorine atom. (3) In the general formula (1), n1 is 0, n2 is 1, Za, Zb and Zc are all single bonds, Q _1, Q ₂ and Q ₃ are all hydrogen atoms (1 )
The pyrimidine derivative according to the above item. (4) The pyrimidine derivative according to item (1), wherein in formula (1), n1 is 1 and n2 is 0. (5) In the general formula (1), (1), wherein n 1 is 0, n ₂ is 1, Za and Zb are each a single bond, and Zc is —COO— or —CF ₂ O—. The pyrimidine derivative according to the above. (6) In the general formula (1), n1 is 0, n2 is 1, Za and Zc are both single bonds, Zb is -COO- or -CF ₂ O-(1) to item The pyrimidine derivative according to the above. (7) The pyrimidine derivative according to the item (1), wherein n1 + n2 = 2 in the general formula (1). (8) In the general formula (1), R is an alkyl group in which one or more hydrogen atoms in the group have been substituted with fluorine.
The pyrimidine derivative according to the above item. (9) A liquid crystal composition comprising at least one pyrimidine derivative according to any one of (1) to (8). (10) As a first component, at least one compound according to any one of (1) to (8) is contained,
As the second component, general formulas (2), (3) and (4)

[0011]

Embedded image

(In each formula, R ₃ , Y ₁ , L ₁ , L ₂ , Z ₁ and Z ₂ may be the same or different among the formulas, and R ₃ is an alkyl group having 1 to 10 carbon atoms. Wherein one or more non-adjacent methylene groups in the alkyl group may be substituted with an oxygen atom or -CH = CH-, and any hydrogen atom in the group may be substituted with a fluorine atom. Y ₁ is a fluorine atom, a chlorine atom, —OCF ₃ , —O
_{CF 2 H, -CF 3, -CF} 2 H, -CFH 2, -OCF 2
CF ₂ H, or show the -OCF ₂ CFHCF _3; L ₁ and L ₂ represents a hydrogen atom or a fluorine atom each independently; Z ₁ and Z ₂ are -CH ₂ each independently CH ₂ -, - C
_{H 2 CH 2 CH 2 CH 2} -, - COO -, - CF 2 O -, -
OCF ₂ —, —CH ＝ CH— or a single bond; ring B is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or a compound in which a hydrogen atom is substituted by a fluorine atom. Shows good 1,4-phenylene; ring C
Represents trans-1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom may be substituted by a fluorine atom; and each atom constituting these compounds may be substituted by its isotope . A) a liquid crystal composition comprising at least one compound selected from the group consisting of: (11) As a first component, it contains at least one compound according to any one of (1) to (8),
As the second component, general formulas (5) and (6)

[0013]

Embedded image

(In each formula, R ₄ and R ₅ each independently represent an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group are an oxygen atom or-
CH = CH- may be substituted with, also hydrogen atoms in the group may be substituted with a fluorine atom; Y ₂ is -C
N represents —C≡C—CN; ring E is trans-1,4-cyclohexylene, 1,4-phenylene, 1,
3-dioxane-2,5-diyl or pyrimidine-
Ring G represents trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene in which a hydrogen atom may be substituted by a fluorine atom; Represents trans-1,4-cyclohexylene or 1,4-phenylene, and Z ₃ represents —CH ₂
CH ₂ -, - COO- or a single bond; L _3, L ₄ and L ₅ each independently represents a hydrogen atom or a fluorine atom; b, c and d each independently is 0 or 1;
In addition, each element constituting these compounds may be substituted with its isotope. A) a liquid crystal composition comprising at least one compound selected from the group consisting of: (12) As a first component, at least one compound according to any one of (1) to (8) is contained,
The second component contains at least one compound selected from the compound group consisting of the general formulas (2), (3) and (4), and the third component has a general formula (7)
(8) and (9)

[0015]

Embedded image

(In each formula, R ₆ , R ₇ , I, J and K may be the same or different between each formula, and R ₆ and R ₇ are each independently an alkyl having 1 to 10 carbon atoms. One or more non-adjacent methylene groups in the alkyl group may be substituted with an oxygen atom or -CH = CH-, and any hydrogen atom in the group may be substituted with a fluorine atom. Ring I, ring J and ring K are each independently trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-, in which a hydrogen atom may be replaced by a fluorine atom. Represents phenylene; Z ₄ and Z ₅
Each independently, -C≡C -, - COO -, - CH 2 C
H ₂ —, —CH ＝ CH— or a single bond; and each atom constituting these compounds may be substituted with its isotope. A) a liquid crystal composition comprising at least one compound selected from the group consisting of: (13) As a first component, at least one compound according to any one of (1) to (8) is contained,
As the second component, at least one compound selected from the compound group consisting of the general formulas (5) and (6) is contained, and as the third component, the general formulas (7), (8) and (9) are included. A liquid crystal composition comprising at least one compound selected from the group consisting of: (14) As a first component, it contains at least one compound according to any one of (1) to (8),
As a part of the second component, at least one compound selected from the compound group consisting of the general formulas (2), (3), and (4) is contained, and as another part of the second component, the general formula (5) ) And at least one compound selected from the compound group consisting of (6), and as a third component, at least a compound selected from the compound group consisting of general formulas (7), (8) and (9) A liquid crystal composition comprising one type. (15) The liquid crystal composition according to any one of the above items (9) to (14), further comprising one or more optically active compounds. The liquid crystal composition according to any one of the above. (16) A liquid crystal display device comprising the liquid crystal composition according to any one of the above items (9) to (15).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the general formula (1) of the present invention has a phenylene group substituted with a hydrogen atom or a halogen-containing electron-withdrawing group at the molecular terminal, and at least one ring other than this ring and a pyrimidine ring. It is a liquid crystal compound having a 1,4-phenylene group substituted with two fluorine atoms and having three or four aromatic rings including a pyrimidine ring. Such a structure has a relatively high voltage holding ratio, a large Δn, and a large Δε, and has excellent low-temperature compatibility with other liquid crystal compounds. For example, the compound (No. 17) belonging to the present invention has the same alkyl chain as the compound (10), but has specifically large Δε and good low-temperature compatibility as described below. Although the physical properties of compound (10) were as described above, Δε was surprising despite the fact that compound (No. 17) of the present invention had an NI transition point of 48.4 ° C. as shown in Example 2. In particular, it is 31.0. As shown in Examples 6 and 7, when dissolved in an existing liquid crystal composition comprising a fluorine-substituted liquid crystal compound, the concentration at which no crystal was generated even after storage at −20 ° C. for 30 days was as follows: In contrast to less than 5%, the content of the compound (No. 17) is 15% or more, indicating that the compound of the present invention has excellent low-temperature compatibility. As shown in Examples 4 and 5, the voltage holding ratio of compound (10) was 2
97.5% at 5 ° C and 92.9% at 100 ° C, whereas the compound (No. 17) has 97.5% and 107.5% at 25 ° C.
It shows almost the same value as 93.2% at 0 ° C. General formula (1)
Some of the compounds of the present invention represented by the formula WO94 /
No. 26840, DE44445224 and Tokuhei Hei 4-
Some are included in the claims of 503818. However, no specific description or data showing physical properties of the compound of the present invention can be found in these prior art documents. Furthermore, there is no description which predicts that the compound of the present invention exhibits the above-mentioned excellent properties.

Now, the compounds of the present invention will be described in more detail. However, no mention is made of a compound in which an element constituting the compound is substituted with an isotope, but the compound substituted with an isotope has no difference from the characteristics shown in the following description.
In the general formula (1), R is a hydrogen atom, or an alkyl group, alkenyl group, alkoxy group having 1 to 20 carbon atoms, in which at least one hydrogen atom in the group may be substituted with a halogen atom, Or an alkoxyalkyl group, from the viewpoint of the balance between low viscosity and high NI transition point, these groups preferably have 1 to 7 carbon atoms, and more preferably 2 to 5 carbon atoms. Compounds in which R is an alkyl group have a better balance of viscosity and NI transition point than compounds in which R is a halogen-substituted alkyl group, but have low-temperature compatibility with other liquid crystal compounds due to the halogen-substituted alkyl group. Is excellent. In a compound in which R is a halogen-substituted alkyl group, R in which one terminal fluorine atom is substituted on the terminal carbon is excellent in balance between viscosity and NI transition point. A compound wherein R is an alkoxy group or an alkoxyalkyl group is
Shows good low-temperature compatibility. Compounds in which R is an alkenyl group have a lower voltage holding ratio than compounds in which R is an alkyl group, but have an excellent balance between the NI transition point and the viscosity. In the general formula (1), n1 and n2 are each independently 0, 1 or 2, and the sum of n1 and n2 is 1 or 2. A compound in which the sum of n1 and n2 is 1 has low viscosity and n
Compounds in which the sum of 1 and n2 is 2 have a high NI transition point. Linking groups Za, Zb and Zc are independently a single bond, _{respectively, -COO -, - CH 2 CH} 2 -, - CH 2 CH 2 C
H ₂ CH ₂ — or —CF ₂ O— is shown, and their characteristics are as follows. Compounds in which the linking groups Za, Zb and Zc are all single bonds have a relatively high NI transition point, low viscosity, excellent compatibility with other liquid crystal compounds or liquid crystal compositions, and chemical It is electrically stable. At least one of linking groups Za, Zb and Zc
Compounds having —CH ₂ CH ₂ — are slightly lower in NI transition point than those in which Za, Zb and Zc are all single bonds, but are more excellent in low-temperature compatibility with other liquid crystal compounds. . At least one of linking groups Za, Zb and Zc
Compounds represented by —COO— are Za, Zb and Zc
Are slightly inferior to those in which all are single bonds, but have a large Δε. Linking groups Za, Zb and Z
at least one is -CH ₂ CH ₂ CH ₂ CH ₂ of c - Compounds that are linking groups Za, Zb and Zc are compared to all single bonds, slightly high but compatibility viscosity further excellent. Linking groups Za, Compound least one is -CF ₂ O-Zb, and Zc are linking groups Za, Zb and Zc are compared to all single bonds, although N-I transition point is low, low It is viscous, has a large Δε, and is chemically and electrically stable.

For the terminal substituent Y, a preferred structure:
The characteristics of the compound having the substituent are shown below. The compound in which Y is F has a relatively large Δε, has a low viscosity, and has excellent compatibility with other liquid crystal compounds or liquid crystal compositions.
Compound Y is -CF ₃ has a very large [Delta] [epsilon]. Y is -OCF ₃ or -OCF ₂ H compounds are low viscosity. _{Y = Cl, -OCF 2 CF 2} H or -O,
The compound that is CF ₂ CFHCF ₃ has a large Δn and a high clearing point. Y is _{-OCH 2 CF 2 H, -OCH 2} C
Compounds that are F ₃ or —OCFHCF ₃ have high NI
It has a transition point and relatively low viscosity. Preferred substituents as Y except the _{above, -CF 2 H, -CF 2 Cl} , -CH
_{2 CF 3, -CH 2 CH 2} F, -CH 2 CH 2 CH 2 F, -C
_{H 2 CH 2 CH 2 CH 2} F, -OCFH 2, -OCF 2 Cl,
—OCF ₂ CF ₃ and —OCF ₂ CF ₂ CF ₃ . 1,4
-The substituents Q _{1 to} Q ₇ to the phenylene group each independently represent a hydrogen atom, a halogen atom or a methyl group,
A compound having a larger number of halogen atoms and methyl groups is more compatible with another liquid crystal compound or a liquid crystal composition, and a compound having a larger number of hydrogen atoms has a higher NI transition point. A compound having a larger number of halogen atoms at the positions of Q ₂ , Q ₅ and Q ₆ has a larger Δε. All of the compounds of the present invention represented by the general formula (1) have a relatively high voltage holding ratio and the above-mentioned features depending on their partial structures.
The compound represented by (1-R) has some preferable characteristics.

[0020]

Embedded image

[0021]

Embedded image

(However, R, Q ₅ , Q ₆ and Y have the same meanings as described above.) The characteristics of the compounds represented by formulas (1-A) to (1-R) will be described. General formulas (1-E), (1-F), (1-
The compounds represented by J), (1-K) and (1-R) are slightly inferior in voltage holding ratio to other compounds,
Each of them has a high voltage holding ratio enough to withstand use in a TFT type liquid crystal display device. Further, since the compounds of the present invention all have a large Δn, they are particularly useful as a liquid crystal material for a liquid crystal display device having a small cell thickness. The compounds represented by formulas (1-A) and (1-B) have low viscosity, large Δε, and good low-temperature compatibility with other liquid crystal compounds. Comparing both, the NI transition point has a high (1-A), Δε has a large (1-B), and the viscosity has a low (1-A). General formulas (1-C) and (1-C)
The compound represented by D) has a large Δε, and particularly has good low-temperature compatibility with other liquid crystal compounds. Comparing the two, the NI transition point is higher in (1-C) and Δε is (1-C).
D) is large and the viscosity is low (1-C). The general formula (1-
The compounds represented by E), (1-F), (1-G) and (1-H) are characterized by extremely large Δε. When these are compared, the NI transition points are higher in (1-E) and (1-F), and the viscosities are (1-G) and (1-H).
Is low. The compound represented by the general formula (1-I) has excellent low-temperature compatibility with other liquid crystal compounds. General formula (1-J),
The compounds represented by (1-K), (1-L) and (1-M) are characterized by extremely large Δε. When these are compared, the NI transition points are (1-J) and (1-J).
K) is high and the viscosity is low for (1-L) and (1-M). Since the compounds represented by the general formulas (1-N) to (1-R) have a very high clearing point, they are useful as components of a liquid crystal material that can be displayed at high temperatures.

There is no compound which has a higher voltage holding ratio, a larger Δε and a larger Δn than the compound of the present invention. Since the compound of the present invention has the above-mentioned features, it particularly requires a high voltage holding ratio and facilitates the production of a liquid crystal display device having a small cell thickness. The compound of the present invention is a liquid crystal compound particularly suitable for a liquid crystal composition for TFT, but may be used for other purposes such as a liquid crystal composition for TN,
Liquid crystal composition for H mode, liquid crystal composition for polymer dispersion type liquid crystal display element, liquid crystal composition for dynamic scattering mode, ST
N liquid crystal composition, ferroelectric liquid crystal composition, antiferroelectric liquid crystal composition, liquid crystal composition for in-plane switching,
The liquid crystal composition for OCB (Optically Compensated Birefringence) mode and the liquid crystal composition for R-OCB mode can be suitably used.

The compound represented by the general formula (1) can be produced by appropriately combining known organic synthetic chemistry techniques. For example, it can be produced by the method described in the fourth edition of Experimental Chemistry Course (Maruzen) and Japanese Patent Publication No. 4-501272. Preferred synthetic procedures for representative compounds are shown below. Formulas (1-A), (1-B), (1
-O).

[0025]

Embedded image

The compound represented by the formula (13) is reacted with urea under acidic conditions, and the resulting product is reacted with a chlorinating reagent such as phosphorus oxychloride to give the compound represented by the formula (13) Is obtained. Grignard reagent (15) prepared from compound (14) and magnesium was converted to NiCl ₂ (dp
By acting on a compound represented by the formula (13) in the presence of (pp), a compound represented by the formula (16) is obtained. The compound (16) is lithiated with a lithiating reagent such as butyllithium, and zinc chloride, Pd (0) and the compound (17) are acted on the lithiated product in this order to obtain a compound represented by the formula (18). . This method is described in J. Org. Chem., 42 , 1821 (19.
77). Also
The method described in J. Chem. Soc. Perkin Trans. 2, 2041 (1989) can also be used. The expression (18) is obtained by the expression (1-A) and the expression (1-
B) and Formula (1-O).

Equations (1-C), (1-D) and (1
A method for synthesizing a compound represented by -P).

[0028]

Embedded image

A compound represented by the formula (20) is obtained in the same manner as in the step of obtaining the compound (16) except that the compound (17) is used instead of the compound (14). Equation (20) is obtained by dividing equation (1-C), equation (1-D), and equation (1-
P). A method for synthesizing a compound represented by the formula (1-E) and the formula (1-F).

[0030]

Embedded image

The compound (16) is lithiated with a lithiating reagent such as butyllithium and the like, and carbon dioxide is allowed to act on the lithiated compound to obtain a compound represented by the formula (21). In the presence of dicyclohexylcarbodiimide and 4- (dimethylamino) pyridine, compound (21) and a compound of formula (22)
By reacting with a phenol derivative represented by the formula (2)
The compound represented by 3) is obtained. Equation (23) is obtained by using equation (1).
-E) and formula (1-F). This method is the fourth
This is the method described in Edition Experimental Chemistry Course, Vol. 22, page 46.
A method for synthesizing compounds represented by the formula (1-G) and the formula (1-H).

[0032]

Embedded image

The compound represented by the formula (24) is obtained by allowing a Lawson reagent to act on the compound (23). The compound represented by the formula (25) is obtained by reacting the compound (24) with a fluorinating reagent such as diethylaminosulfur trifluoride (DAST) or a pyridine solution of hydrofluoric acid. Equation (25) includes equations (1-G) and (1-H). A method for synthesizing a compound represented by the formula (1-I).

[0034]

Embedded image

A compound represented by the formula (28) is obtained in the same manner as in the step for obtaining the compound (18) except that the compound (26) is used instead of the compound (14). Equation (28) includes equation (1-I). A method for synthesizing the compounds represented by the formulas (1-J) and (1-K).

[0036]

Embedded image

A compound represented by the formula (29) can be obtained in the same manner as in the step of obtaining the compound (21) except that the compound (13) is used instead of the compound (16). Except that the phenol derivative (30) having a protected hydroxyl group is used instead of the compound (16), the compound (1)
The compound represented by the formula (31) is obtained in the same manner as in the step of obtaining 8). The compound represented by the formula (32) is obtained by treating the compound (31) with an acid. Compound (29) is used in place of compound (21), and compound (2)
A compound represented by the formula (33) is obtained in the same manner as in the step of obtaining the compound (23) except that the compound (32) is used instead of 2). Equation (33) includes equations (1-J) and (1-K). A method for synthesizing a compound represented by the formula (1-L) and the formula (1-M).

[0038]

Embedded image

A compound represented by the formula (35) is obtained in the same manner as in the step for obtaining the compound (25) except that the compound (33) is used instead of the compound (23). Formula (33) includes formula (1-L) and formula (1-M). A method for synthesizing a compound represented by the formula (1-N).

[0040]

Embedded image

A compound represented by the formula (36) is obtained in the same manner as in the step for obtaining the compound (18) except that the compound (14) is used instead of the compound (17). A compound of the formula (37) described in the same manner as in the step of obtaining the compound (18), except that the compound (36) is used instead of the compound (16).
The compound represented by is obtained. Equation (37) is obtained by calculating equation (1-
N). A method for synthesizing a compound represented by the formula (1-R).

[0042]

Embedded image

A compound represented by the formula (39) is obtained in the same manner as in the step for obtaining the compound (23) except that the compound (36) is used instead of the compound (16). Formula (39) includes Formula (1-R).

The liquid crystal composition of the present invention preferably contains one or more compounds represented by the general formula (1) at a ratio of 0.1 to 99.9% by weight in order to exhibit excellent characteristics. More preferably, the ratio is 1 to 50% by weight, further preferably 3 to 20% by weight. The liquid crystal composition provided by the present invention includes a first component containing at least one compound represented by the general formula (1),
Compounds selected from the compound group represented by (9) according to the purpose of the liquid crystal composition are mixed to complete the composition. Preferred examples of the compounds represented by formulas (2) to (4) used in the liquid crystal composition of the present invention include the following compounds.

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

(R3 and Y1 have the same meanings as described above.) The compounds represented by the general formulas (2) to (4) are compounds having a positive dielectric anisotropy value, and have thermal stability and This compound is extremely useful when preparing a liquid crystal composition for a TFT that requires high reliability such as excellent chemical stability and high voltage holding ratio (or high specific resistance value). TF
When preparing a liquid crystal composition for T, the general formula (2)
The compound represented by (4) can be used in a range of 1 to 99% by weight based on the total weight of the liquid crystal composition, but is preferably 10% by weight.
９７97% by weight, more preferably 40-95% by weight. At that time, the compounds represented by the general formulas (7) to (9) may be further contained for the purpose of adjusting the viscosity. S
When preparing a liquid crystal composition for TN or TN,
Compounds represented by general formulas (2) to (4) can be used.
Preferred examples of the compounds represented by formulas (5) and (6) used in the liquid crystal composition of the present invention include the following compounds.

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

(Wherein, R ₄ , R ₅ , and Y ₂ have the same meanings as described above.) The compounds represented by the general formulas (5) and (6) have a positive dielectric anisotropy value and have a positive dielectric anisotropy value. It is used for the purpose of decreasing the threshold voltage of the liquid crystal composition, especially because of its large value. It is also used for the purpose of adjusting the value of the refractive index anisotropy and expanding the nematic range such as increasing the clearing point. Further, it is also used for the purpose of improving the steepness of the voltage-transmittance curve of the liquid crystal compositions for STN and TN. The compounds represented by the general formulas (5) and (6) are particularly useful when preparing liquid crystal compositions for STN and TN. When the amount of the compound represented by the general formulas (5) and (6) increases in the liquid crystal composition, the threshold voltage of the liquid crystal composition decreases, but the viscosity increases. Therefore, as long as the viscosity of the liquid crystal composition satisfies the required value, it is advantageous to use a large amount because the liquid crystal composition can be driven at a low voltage. When preparing a liquid crystal composition for STN or TN, the compounds represented by the general formulas (5) and (6) are in the range of 0.1 to 99.9% by weight based on the total weight of the liquid crystal composition. , But is preferably from 10 to 97% by weight, more preferably from 40 to 95% by weight. Preferred examples of the compounds represented by formulas (7) to (9) used in the liquid crystal composition of the present invention include the following compounds.

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

(R ₆ and R ₇ have the same meaning as described above.) The compounds represented by the general formulas (7) to (9) have a small absolute value of dielectric anisotropy and are close to zero. It is. The compound of the general formula (7) is mainly used for adjusting the viscosity or adjusting the refractive index anisotropy value. Further, the compounds represented by the general formulas (8) and (9) are used for the purpose of widening the nematic range such as increasing the clearing point or adjusting the refractive index anisotropy value. Formula (7)-
When the amount of the compound represented by (9) increases, the threshold voltage of the liquid crystal composition increases, but the viscosity decreases. Therefore, it is desirable to use a large amount as long as the threshold voltage of the liquid crystal composition satisfies the required value. When preparing a liquid crystal composition for a TFT, general formulas (7) to (9)
The amount of the compound represented by is preferably 40% by weight or less, more preferably 35% by weight or less. ST
When preparing a liquid crystal composition for N or TN, 70
% By weight or less, more preferably 60% by weight or less.

In the present invention, except for a special case such as a liquid crystal composition for an OCB mode, a helical structure of the liquid crystal composition is usually induced to adjust a necessary twist angle, and a reverse twist (reverse twist) is obtained.
For the purpose of preventing verse twist), an optically active compound is added. For this purpose, any known optically active compounds can be used. Preferred examples include the following optically active compounds (Op-1) to (Op-8).

[0066]

Embedded image

In the liquid crystal composition of the present invention, these optically active compounds are usually added to adjust the twist pitch.
The twist pitch is preferably adjusted in the range of 40 to 200 μm for a liquid crystal composition for TFT and TN. In the case of a liquid crystal composition for STN, it is preferable to adjust the composition to a range of 6 to 20 μm. In addition, bistable TN (Bistable
TN) In the case of a liquid crystal composition for a mode, 1.5 to 4 μm
It is preferable to adjust to the range of m. Further, two or more optically active compounds may be added for the purpose of adjusting the temperature dependency of the pitch.

The liquid crystal composition of the present invention is prepared by adding a dichroic dye such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine to the guest host ( GH)
It can also be used as a liquid crystal composition for a mode. Or,
NC made by encapsulating nematic liquid crystal
It can also be used as a liquid crystal composition for a polymer dispersed liquid crystal display (PDLCD) represented by a polymer network liquid crystal display (PNLCD) in which a three-dimensional network polymer is prepared in an AP or liquid crystal. In addition, birefringence control (EC
It can also be used as a liquid crystal composition for B) mode or dynamic scattering (DS) mode.

The liquid crystal composition of the present invention is prepared by a conventional method. Generally, a method of dissolving various components at a high temperature is used. The following composition examples (composition examples 1 to 18) are shown as examples of the liquid crystal composition containing the liquid crystal compound of the present invention. In each of the composition examples, the compound is represented by a left terminal group, a bonding group,
Each part of the ring structure and the right terminal group is symbolized and described.
Compound No. attached to the compound of the present invention. Is the same as that shown in the embodiment described later. In the composition examples and examples, “%” means “% by weight” unless otherwise specified. The physical property data of the composition examples are TNI (NI transition point or clearing point: ° C.), η (viscosity: measurement temperature 20.0 ° C.).
° C), Δn (refractive index anisotropy value: measuring temperature 25.0 ° C),
Δε (dielectric anisotropy value: measuring temperature 25.0 ° C.) and V
th (threshold voltage: measured temperature: 25.0 ° C.).

[0070]

Embedded image

Composition Example 1 5-PyB (F, F) B (F) -OCF3 (No. 17) 14.0% 1V2-BEB (F, F) -C 5.0% 3-HB-C25 1.0% 1-BTB-3 5.0% 2-BTB-1 10.0% 3-HH-4 11.0% 3-HHB-1 11.0% 3-HHB-3 9.0% 3- H2BTB-2 4.0% 3-HB (F) TB-2 6.0% TNI = 76.7 (° C.) Δn = 0.151 Δε = 11.4 Vth = 1.90 (V) The above composition 100 Optically active compound (OP-4) in parts by weight
Of the composition to which 0.8 part was added was 10.5 μm.

Composition Example 2 5-PyB (F) B (F, F) -F (No. 1) 5.0% 3-PyB (F, CL) B-CL (No. 19) 5.0% 4-B (F, F) PyB (F) -OCF2CF2H (No. 37) 5.0% 2O1-BEB (F) -C 5.0% 3O1-BEB (F) -C 15.0% 4O1-BEB (F) -C 13.0% 5O1-BEB (F) -C 13.0% 2-HHB (F) -C 15.0% 3-HB (F) TB-2 4.0% 3-HB ( F) TB-3 4.0% 3-HB (F) TB-4 4.0% 3-HHB-1 8.0% 3-HHB-O1 4.0%

Composition Example 3 3-B (F) B (F) PyB-F (No. 135) 5.0% 5-PyB (F) EB (F, F) -F (No. 41) 0% 3-BEB (F) -C 8.0% 3-HB-C 8.0% V-HB-C 8.0% 1V-HB-C 8.0% 3-HB-O2 3.0% 3-HH-2V 14.0% 3-HH-2V1 7.0% V2-HHB-1 15.0% 3-HHB-1 5.0% 3-HHEB-F 7.0% 3-H2BTB-2 6.0%

Composition Example 4 4-BPyB (F, F) B (F) -F (No. 142) 2.0% 7-B (F) PyB (F) -CF3 (No. 26) 2.0 % V2-HB-C 12.0% 1V2-HB-C 12.0% 3-HB-C 15.0% 3-H (1D, 2D, 3D) BC 9.0% 3-HB (F ) -C 5.0% 2-BTB-1 2.0% 3-HH-4 8.0% 3-HH-VFF 6.0% 2-H (1D, 2D, 3D) HB-C 3.0 3-HHB-C 6.0% 3-HB (F) TB-2 8.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0%

Composition Example 5 4-HPyB (F) B (F) -F (No. 150) 3.0% 2-PyB (F, F) CF2OB (F) -F (No. 74) 2.0 % 3-PyEB (F, F) B (F, F) -OCF3 (No. 92) 2.0% 1-PyCF2OB (F) BF (No. 108) 2.0% 5-BEB (F) -C 5.0% V-HB-C 11.0% 5-PyB-C 6.0% 4-BB-3 11.0% 3-HH-2V 10.0% 5-HH-V 11.0 % V-HHB-1 7.0% V2-HHB-1 15.0% 1V2-HBB-2 10.0% 3-HHEBH-3 5.0%

Composition Example 6 5-PyB (F, F) B (F, F) EB (F) -OCF2CFHCF3 (No. 156) 4.0% 5-PyB (F, F) B (F, F) B (F) -CL (No. 129) 4.0% 1V2-BEB (F, F) -C 8.0% 3-HB-C 10.0% V2V-HB-C 14.0% V2V-HH -3 19.0% 3-HB-O2 4.0% 3-HHB-1 10.0% 3-HHB-3 15.0% 3-HB (F) TB-2 4.0% 3-HB ( F) TB-3 4.0% 3-H2BTB-2 4.0%

Composition Example 7 F5-PyB (F, F) B (F) -F (No. 10) 6.0% V2-HB-TC 10.0% 3-HB-TC 10.0% 3- HB-C 10.0% 5-HB-C 7.0% 5-BB-C 3.0% 2-BTB-1 10.0% 2-BTB-O1 5.0% 3-HH-4 0% 3-HHB-1 10.0% 3-HHB-3 11.0% 3-H2BTB-2 3.0% 5-BTB (F) TB-3 10.0%

Composition Example 8 5-PyB (F, F) B (F) -OCF3 (No. 17) 8.0% 1V2-BEB (F, F) -C 6.0% 3-HB-C 18 0.0% 2-BTB-1 10.0% 5-HH-VFF 30.0% 1-BHH-VFF 8.0% 1-BHH-2VFF 11.0% 3-H2BTB-2 5.0% 3- HHB-1 4.0% TNI = 73.1 (° C) Δn = 0.124 Δε = 9.0 Vth = 1.73 (V)

Composition Example 9 5-PyB (F, F) B (F) -OCF3 (No. 17) 13.0% 2-HHB (F) -F 17.0% 3-HHB (F) -F 17.0% 5-HHB (F) -F 16.0% 2-H2HB (F) -F 10.0% 3-H2HB (F) -F 5.0% 5-H2HB (F) -F 0% 2-HBB (F) -F 6.0% 3-HBB (F) -F 6.0% TNI = 94.5 (° C) Δn = 0.098 Δε = 8.1 Vth = 1.82 ( V) 100 parts by weight of the above composition was added to an optically active compound (OP-
The pitch of the composition containing 0.3 part by weight of 8) was 79.0.
μm.

Composition Example 10 5-PyB (F) B (F, F) -F (No. 1) 4.0% 3-HB-CL 10.0% 5-HB-CL 4.0% 7- HB-CL 4.0% 1O1-HH-5 5.0% 2-HBB (F) -F 8.0% 3-HBB (F) -F 8.0% 5-HBB (F) -F 14. 0% 4-HHB-CL 8.0% 5-HHB-CL 8.0% 3-H2HB (F) -CL 4.0% 3-HBB (F, F) -F 10.0% 5-H2BB ( F, F) -F 9.0% 3-HB (F) VB-2 4.0%

Composition Example 11 3-PyB (F, CL) B-CL (No. 19) 5.0% 4-B (F, F) PyB (F) -OCF2CF2H (No. 37) 5.0% 7-B (F) PyB (F) -CF3 (No. 26) 5.0% 5-PyB (F) EB (F, F) -F (No. 41 5.0% 3-HHB (F, F) ) -F 9.0% 3-H2HB (F, F) -F 8.0% 4-H2HB (F, F) -F 8.0% 5-H2HB (F, F) -F 8.0% 3 -HBB (F, F) -F 21.0% 3-H2BB (F, F) -F 10.0% 5-HHBB (F, F) -F 3.0% 5-HHEBB-F 2.0% 3-HH2BB (F, F) -F 3.0% 1O1-HBBH-4 4.0% 1O1-HBBH-5 4.0%

Composition Example 12 2-PyB (F, F) CF2OB (F) -F (No. 74) 5.0% 3-PyEB (F, F) B (F, F) -OCF3 (No. 92) 4.0) 1-PyCF2OB (F) BF (No. 10) 4.0% 5-PyB (F, F) B (F, F) B (F) -CL (No. 129) 0% 3-B (F) B (F) PyB-F (No. 135) 4.0% 5-HB-F 12.0% 6-HB-F 9.0% 7-HB-F 7.0 % 5-HHB-OCF3 5.0% 3-HH2B-OCF3 4.0% 5-HH2B-OCF3 4.0% 3-HHB (F, F) -OCF3 5.0% 3-HBB (F) -F 10.0% 5-HBB (F) -F 10.0% 3-HH2B (F) -F 3.0% 3-HB (F) BH-3 3.0% 5- BBH-3 3.0% 3-HHB (F, F) -OCF2H 4.0%

Composition Example 13 4-BPyB (F, F) B (F) -F (No. 142) 3.0% 4-HPyB (F) B (F) -F (No. 150) 3.0 % 3-H2HB (F, F) -F 7.0% 5-H2HB (F, F) -F 8.0% 3-HHB (F, F) -F 10.0% 4-HHB (F, F ) -F 5.0% 3-HH2B (F, F) -F 9.0% 5-HH2B (F, F) -F 9.0% 3-HBB (F, F) -F 15.0% 5 -HBB (F, F) -F 15.0% 3-HBEB (F, F) -F 2.0% 4-HBEB (F, F) -F 2.0% 5-HBEB (F, F)- F 2.0% 3-HHEB (F, F) -F 10.0%

Composition Example 14 F5-PyB (F, F) B (F) -F (No. 10) 8.0% 5-PyB (F, F) B (F, F) EB (F) OCF2CFHCF3 ( No. 156) 4.0% 7-HB (F) -F 5.0% 5-H2B (F) -F 5.0% 3-HB-O2 10.0% 3-HH-4 2.0% 3-HH (5D, 6D, 7D) -4 3.0% 2-HHB (F) -F 10.0% 3-HHB (F) -F 10.0% 5-HH (5D, 6D, 7D) B (F) F 10.0% 3-H2HB (F) -F 5.0% 2-HBB (F) -F 3.0% 3-HBB (F) -F 3.0% 5-HBB (F ) -F 6.0% 2-H2BB (F) -F 5.0% 3-H2BB (F) -F 6.0% 3-HHB-O1 5.0%

Composition Example 15 5-PyB (F, F) B (F) -OCF3 (No. 17) 12.0% 7-HB (F, F) -F 3.0% 3-H2HB (F, F) -F 12.0% 4-H2HB (F, F) -F 10.0% 5-H2HB (F, F) -F 10.0% 3-HHB (F, F) -F 5.0% 4-HHB (F, F) -F 5.0% 3-HH2B (F, F) -F 15.0% 5-HH2B (F, F) -F 10.0% 3-HBB (F, F) -F 12.0% 3-HBCF2OB (F, F) -F 6.0% TNI = 71.9 (° C) Δn = 0.092 Δε = 11.1 Vth = 1.43 (V) The above composition 100 parts by weight of an optically active compound (OP-
The pitch of the composition containing 0.25 parts by weight of (5) is 63.
It was 0 μm.

Composition Example 16 5-PyB (F, F) B (F) -OCF3 (No. 17) 10.0% 7-HB (F, F) -F 5.0% 3-H2HB (F, F) -F 12.0% 4-H2HB (F, F) -F 10.0% 3-HHB (F, F) -F 10.0% 4-HHB (F, F) -F 5.0% 3-HBB (F, F) -F 10.0% 4-HHEB (F, F) -F 3.0% 5-HHEB (F, F) -F 3.0% 2-HBEB (F, F) -F 3.0% 3-HBEB (F, F) -F 5.0% 5-HBEB (F, F) -F 3.0% 3-HDB (F, F) -F 15.0% 3- HHBB (F, F) -F 6.0% TNI = 70.9 (° C) Δn = 0.093 Δε = 15.1 Vth = 1.29 (V)

Composition Example 17 5-PyB (F, F) B (F) -OCF3 (No. 17) 5.0% 5-PyB (F) B (F, F) -F (No. 1) 5 5.0% 5-H4HB (F, F) -F 7.0% 5-H4HB-OCF3 15.0% 3-H4HB (F, F) -CF3 8.0% 3-HB-CL 6.0% 5 -HB-CL 4.0% 2-H2BB (F) -F 5.0% 3-H2BB (F) -F 10.0% 5-HVHB (F, F) -F 5.0% 3-HHB- OCF3 5.0% 3-H2HB-OCF3 5.0% V-HHB (F) -F 5.0% 3-HHB (F) -F 5.0% 5-HHEB-OCF3 2.0% 3-HBEB (F, F) -F 5.0% 5-HH-V2F 3.0%

Composition Example 18 5-PyB (F, F) B (F) -OCF3 (No. 17) 8.0% 5-HB-CL 12.0% 3-HH-4 7.0% 3- HB-O2 20.0% 3-H2HB (F, F) -F 8.0% 3-HBB (F, F) -F 6.0% 2-HHB (F) -F 5.0% 3-HHB (F) -F 5.0% 5-HHB (F) -F 5.0% 2-H2HB (F) -F 2.0% 3-H2HB (F) -F 1.0% 5-H2HB (F ) -F 2.0% 3-HHBB (F, F) -F 4.0% 3-HBCF2OB-OCF3 4.0% 5-HBCF2OB (F, F) -CF3 4.0% 3-HHB-13 0.0% 3-HHB-O1 4.0% TNI = 69.6 (° C.) Δn = 0.093 Δε = 5.8 Vth = 1.99 (V)

[0089]

The present invention will be described in more detail with reference to the following examples. In each example, C indicates a crystal, S _A indicates a smectic A phase, N indicates a nematic phase, and I indicates an isotropic liquid phase.

Example 1 2- (4- (3-fluoro-4-trifluoromethoxyphenyl) -3,5-difluorophenyl) -5-pentylpyrimidine (in the formula (1), R = n-pentyl group , N1 = 0, n2 = 1, ring B = (a), Za = Zb
= Zc = single bond, Q ₁ = Q ₃ = Q ₄ = Q ₆ = Q ₇ = hydrogen atom, Q ₂ = Q ₅ = fluorine atom, Y = OCF ₃ (No. 17)).

(First step) 11.48 kg of phosphorus oxychloride
(74.9 mol) in dimethylformamide (DMF)
Add at 18.degree. C. to 18.74 Kg, and
Stirred for hours. A solution of 6.0 kg (31.9 mol) of 1,1-diethoxyheptane in 25 l of dichloromethane was added to this viscous solution at 10 ° C., and the mixture was stirred at the same temperature for 2 hours, and then heated to 70 ° C. over 30 minutes. did. After cooling the reaction solution, 33.2 kg of potassium carbonate and 100 l of water were used.
The solution was gradually added to an aqueous solution consisting of not more than 30 ° C., and stirred at room temperature for 5 hours. The product was extracted with chloroform. The extract was washed with brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by distillation to obtain 2.6 kg (15.3 mol) of 2-ethoxymethylidenylheptanal. The yield was 48%.

(Second stage) 1197 g (7.03 mol) of the above 2-ethoxymethylidenylheptanal and urea 5
07 g (8.44 mol) were stirred in 1 liter of ethanol for 5 minutes, this was cooled to 0 ° C. and then 12N-
After dropwise adding 1 liter of hydrochloric acid, the suspension was heated to reflux for 6 hours. After cooling, the reaction solution was neutralized with a 2N aqueous solution of sodium hydroxide, and the product was extracted with chloroform. After the extract was washed with water and dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was recrystallized from toluene to give 2
972 g of -hydroxy-5-pentylpyrimidine (5.
86 mol). Its yield from 2-ethoxymethylidenylheptanal was 83%.

(Third stage) The above-mentioned 2-hydroxy-5-pentylpyrimidine 12 was dissolved in 500 ml of phosphorus oxychloride.
0.4 g (0.724 mol) was added, and the mixture was heated under reflux for 5 hours. Excess phosphorus oxychloride was distilled off under reduced pressure, and the residue was added to ice water. The product was extracted with toluene. The extract was washed with 2N-sodium hydroxide and water in this order, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by distillation to obtain 76.3 g (0.413 mol) of 2-chloro-5-pentylpyrimidine. The yield was 57%.

(Fourth stage) 200 ml of tetrahydrofuran
In the above, a Grignard reagent was prepared from dried magnesium and 49.0 g (254 mmol) of 3,5-difluorobromobenzene, 1 g of NiCl ₂ (dppp) was added thereto, and then the above 2-chloro-5-pentyl was added. 36.0 g (195 mmol) of pyrimidine was added dropwise, and the mixture was heated under reflux for 2 hours. After cooling, the reaction mixture was added to 200 ml of 1N hydrochloric acid, and the product was extracted with ether. The extract was washed with saturated aqueous sodium hydrogen carbonate and water in this order, dried over anhydrous magnesium, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: heptane / toluene = 1/1) to give 2- (3,5-difluorophenyl) -5-pentylpyrimidine (8.0 g, 30 g).
mmol). The yield was 15%.

(Fifth Stage) 8.0 g of the above 2- (3,5-difluorophenyl) -5-pentylpyrimidine (30 g)
mmol) in 80 ml of THF under a nitrogen atmosphere.
Cooled to 60 ° C. To this solution, 20 ml (32 mmol) of a 1.60 M hexane solution of n-butyllithium was added dropwise while keeping the liquid temperature not exceeding −50 ° C., and the mixture was stirred at that temperature for 1 hour. Next, 64 ml (32 mmol) of a 0.5 M THF solution of zinc chloride was added dropwise to the reaction solution while keeping the solution temperature not exceeding −50 ° C., followed by heating to room temperature and stirring for 30 minutes. 0.5 g of tetrakistriphenylphosphine palladium and 8.3 g of 3-fluoro-4-trifluoromethoxybromobenzene were added to this solution.
(32 mmol) and heated under reflux for 3 hours. 100 ml of water was added to the reaction solution, and the product was extracted with toluene. The extract was washed successively with 3N hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated saline, dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography (developing solvent: heptane / toluene = 1/1) and then recrystallized twice using heptane / ethyl acetate = 1/1 to give 2- (4- (3 -Fluoro-4-trifluoromethoxyphenyl) -3,5-difluorophenyl) -5-pentylpyrimidine 0.09 g (0.2
mmol). Its yield from 2- (3,5-difluorophenyl) -5-pentylpyrimidine was 0.7%. 1H-NMR (CDCl ₃ ) δ (ppm): 8.65
(S, 2H), (8.21 to 7.98 (m, 2H),
7.50 to 7.36 (m, 3H), 2.66 (t, 2
H) 1.79-1.27 (m, 6H), 0.92
(T, 3H). C-S _A point 66.9 ° C, S _A- I point 82.1 ° C.

Based on the description in Example 1 and the column of the detailed description of the invention, the following compound No. 1 to No. 170
Can be manufactured. In addition, the compound of Example 1 was repeated.

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

Example 2 (Use Example 1) 4- (4-propylcyclohexyl) benzonitrile 24% 4- (4-pentylcyclohexyl) benzonitrile 36% 4- (4-heptylcyclohexyl) benzonitrile 25% 4- ( A liquid crystal composition (A) comprising 15% of 4- (4-pentylcyclohexyl) phenyl) benzonitrile was prepared. This nematic liquid crystal composition has the following physical property values. TNI = 71.7 ° C., Vth = 1.79 V (measured at a cell thickness of 9.2 μm) Δε = 11.0, Δn = 0.137. The compound of Example 1 2- (4- (3-fluoro-4-trifluoromethoxyphenyl) -3,5-difluorophenyl) -5 was added to 85% by weight of the liquid crystal composition (A1).
15% by weight of pentylpyrimidine (Compound No. 17)
The mixture was mixed to prepare a liquid crystal composition (B). The physical properties were as follows. TNI = 68.2 ° C., Vth = 1.47 V (measured at 8.9 μm cell thickness) Δε = 14.0, Δn = 0.142. The composition (B) exhibited a nematic phase even after being left at −20 ° C. for 30 days.
Physical properties of 7) were as follows. TNI = 48.4 ° C., Δε = 31.0, Δn = 0.170

Example 3 (Comparative Example 1) 85% by weight of the liquid crystal composition (A) and JP-A-2-2336
A liquid crystal composition (BR) comprising 15% by weight of 2- (4- (3,4,5-trifluorophenyl) phenyl) -5-pentylpyrimidine (compound (10)) described in No. 26 was prepared. Prepared. The physical properties were as follows. TNI = 73.5 ° C. Vth = 1.60 V (measured at a thickness of 9.3 μm) Δε = 12.3 Δn = 0.147. When this composition (BR) was stored at -20 ° C, crystals appeared on the fifth day. The compound (10) calculated by extrapolation from the physical properties and composition of the liquid crystal composition (BR)
Were as follows. TNI = 83.7 ° C. Δε = 18.7 Δn = 0.204 From these results, it was found that Compound No. of the present invention was compared with Compound (10). 17 shows that although the NI transition point is about 10 ° C. lower, Δε is about 1.7 times as large, and the low-temperature compatibility with other liquid crystals is also good.

Example 4 4- (2- (4-ethylcyclohexyl) ethyl) cyclohexyl-3,4-difluorobenzene 40% 4- (2- (4-propylcyclohexyl) ethyl) cyclohexyl-3,4-difluorobenzene A liquid crystal composition (C) comprising 20% of 40% of 4- (2- (4-pentylcyclohexyl) ethyl) cyclohexyl-3,4-difluorobenzene was prepared. 90% by weight of this liquid crystal composition (C) and 2- (4- (3-fluoro-4-trifluoromethoxyphenyl) -3,5-difluorophenyl) -5-pentylpyrimidine (Compound No. 1)
7) A liquid crystal composition (D) consisting of 10% by weight was prepared. The voltage holding ratio of this liquid crystal composition (D) was 9 at 25 ° C.
7.5% and 93.2% at 100 ° C.

Example 5 (Comparative Example 2) 90% by weight of the liquid crystal composition (C) and 2- (4- (3,3)
A liquid crystal composition (DR) was prepared which consisted of 10% by weight of (4,5-trifluorophenyl) phenyl) -5-pentylpyrimidine (compound (10)). Its voltage holding ratio was 97.5% at 25 ° C and 92.9% at 100 ° C. Therefore, the voltage holding ratio of the compound (No. 17) of the present invention is the compound (10) which is an existing pyrimidine derivative.
It turns out that there is no inferiority compared with.

Example 6 85% by weight of the liquid crystal composition (C) and 2- (4- (3
-Fluoro-4-trifluoromethoxyphenyl)-
3,5-Difluorophenyl) -5-pentylpyrimidine (Compound No. 17) in an amount of 15% by weight to prepare a liquid crystal composition (D2). The product exhibited a nematic phase even after being left at −20 ° C. for 30 days.

Example 7 (Comparative Example 3) 95% by weight of the liquid crystal composition (C) and 2- (4- (3-
5% by weight of fluoro-4-trifluoromethoxyphenyl) phenyl) -5-pentylpyrimidine (compound 10)
A liquid crystal composition (D2-R) consisting of When this was left at -20 ° C for 30 days, crystals appeared. Therefore, it can be seen that the low-temperature compatibility of the compound (No. 17) of the present invention with the fluorine-substituted liquid crystal compound is superior to that of the known compound (10).

[0120]

The compounds of the present invention each have a large Δε
And a relatively high voltage holding ratio of Δn, and good low-temperature compatibility with other liquid crystal compounds. By using the compound of the present invention as a component of the liquid crystal composition, it is possible to produce a TFT type liquid crystal display device having a thinner cell thickness.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Kago Tomi 2-17-17 Tatsumidaihigashi, Ichihara-shi, Chiba (72) Inventor Fusayuki Takeshita 939-5 Nakatomi, Kimitsu-shi, Chiba 5 (72) Inventor Etsuo Nakagawa Chiba 8890 Goi, Ichihara

Claims (16)

[Claims] 1. A compound of the general formula (1) (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. One or more hydrogen atoms in the alkyl group may be substituted with a halogen atom, and one or more hydrogen atoms in the group may be substituted. of -CH ₂ - is an oxygen atom or -CH ₂ = CH ₂ - may be substituted with, but instead that the oxygen atom adjacent; n1 and n2 are each independently 0, 1 or 2,
Wherein the sum of n1 and n2 is 1 or 2; ring A and ring B are each independently 1,4-phenylene, a fluorine-substituted 1,4-phenylene represented by formula (a), or 1,4-cyclohexylene, wherein ring A and ring B
At least one of the fluorine-substituted 1, represented by the formula (a)
N 1 and / or n 2 corresponding to the fluorine-substituted 1,4-phenylene are 1 or 2
1,4-cyclohexylene may have one or more non-adjacent —CH ₂ — in the group optionally substituted with an oxygen atom, and 1,4-cyclohexylene has one or more A hydrogen atom may be replaced by a halogen atom;
a, Zb, and Zc are each independently a single bond,-
_{CH 2 CH 2 -, - COO} -, - CF 2 O- or -C
_{H 2 CH 2 CH 2 CH 2} - _{indicates; Q 1, Q 2, Q} 3, Q 4, Q
₅ , Q ₆ and Q ₇ each independently represent a hydrogen atom, a halogen atom or a methyl group, but when at least one of Za, Zb and Zc is —CH ₂ CH ₂ —, Q ₂ is a fluorine atom Y represents a hydrogen atom, a halogen atom, or a halogenated alkyl group having 1 to 5 carbon atoms, wherein one or more non-adjacent methylene groups in the halogenated alkyl group are substituted with an oxygen atom or a sulfur atom. And each element constituting the compound may be substituted with its isotope. A) a pyrimidine derivative represented by the formula: 2. A general formula (1), n1 is 0, n2 is 1, Za, a Zb and Zc are all single bonds, Q ₁ and Q ₃ are both hydrogen atoms, Q ₂ The pyrimidine derivative according to claim 1, wherein is a fluorine atom. 3. In the general formula (1), n1 is 0, n2 is 1, Za, Zb and Zc are all single bonds, and Q ₁ , Q ₂ and Q ₃ are all hydrogen atoms. The pyrimidine derivative according to claim 1. 4. The pyrimidine derivative according to claim 1, wherein in formula (1), n1 is 1 and n2 is 0. 5. The general formula (1), n1 is 0, n ₂ is 1, Za and Zb are both single bonds, claim Zc is -COO- or -CF ₂ O-a is 2. The pyrimidine derivative according to 1. 6. In the general formula (1), n1 is 0, n2 is 1, Za and Zc are each a single bond, and Zb is —COO— or —CF ₂ O—. The pyrimidine derivative according to the above. 7. The pyrimidine derivative according to claim 1, wherein in the general formula (1), n1 + n2 = 2. 8. The pyrimidine derivative according to claim 1, wherein in the general formula (1), R is an alkyl group in which one or more hydrogen atoms in the group have been substituted with fluorine atoms. 9. A liquid crystal composition comprising at least one pyrimidine derivative according to any one of claims 1 to 8. 10. The first component contains at least one pyrimidine derivative according to any one of claims 1 to 8, and the second component has a general formula (2), (3) or (4). Embedded image (In each formula, R ₃ , Y ₁ , L ₁ , L ₂ , Z ₁ and Z ₂ may be the same or different between each formula, and R ₃ is an alkyl group having 1 to 10 carbon atoms; One or more non-adjacent methylene groups in the alkyl group may be an oxygen atom or -CH
ＣＨCH— and any hydrogen atom in this group may be replaced by a fluorine atom; Y ₁ is a fluorine atom, a chlorine atom, —OCF ₃ , —OCF ₂ H, —CF
_{3, -CF 2 H, -CFH 2} , -OCF 2 CF 2 H, or show the -OCF ₂ CFHCF _3; L ₁ and L ₂ each independently represents a hydrogen atom or a fluorine atom; Z ₁ and Z ₂ -CH ₂ CH ₂ independently each _{-, - CH 2 CH 2 CH} 2 CH 2
-, - COO -, - CF 2 O -, - OCF 2 -, - CH =
CH- or a single bond; Ring B is trans-1,4
-Cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylene in which a hydrogen atom can be replaced by a fluorine atom; ring C is trans-1,4-
Cyclohexylene or 1,4-phenylene in which a hydrogen atom may be substituted by a fluorine atom; and each atom constituting these compounds may be substituted by its isotope. A) a liquid crystal composition comprising at least one compound selected from the group consisting of: 11. A compound comprising at least one compound according to any one of claims 1 to 8 as a first component,
As the second component, general formulas (5) and (6) (In each formula, R ₄ and R ₅ are each independently a C 1-10
Wherein one or more non-adjacent methylene groups in the alkyl group are an oxygen atom or -CH = CH-
And a hydrogen atom in this group may be replaced by a fluorine atom; Y ₂ represents —CN, or —.
Ring E represents trans-1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; ring G represents Is trans-1,4-cyclohexylene,
Pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be replaced by a fluorine atom; ring H represents trans-1,4-cyclohexylene or 1,4-phenylene, and Z ₃ It is -CH ₂ CH ₂ -, -
L ₃ , L ₄ and L ₅ each independently represent a hydrogen atom or a fluorine atom; b, c and d each independently represent 0 or 1; May be substituted by its isotope. A) a liquid crystal composition comprising at least one compound selected from the group consisting of: 12. A compound comprising at least one compound according to claim 1 as a first component,
The second component contains at least one compound selected from the compound group consisting of the general formulas (2), (3) and (4), and the third component has a general formula (7)
(8) and (9) (In each formula, R ₆ , R ₇ , I, J and K may be the same or different between each formula, and R ₆ and R ₇ each independently represent an alkyl group having 1 to 10 carbon atoms. One or more non-adjacent methylene groups in the alkyl group may be substituted with an oxygen atom or -CH = CH-, and any hydrogen atom in the group may be substituted with a fluorine atom. Ring I, ring J and ring K each independently represent trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted by a fluorine atom; ; Z ₄ and Z ₅ are each independently, -C≡C -, - COO -, - CH 2 CH 2 -, - CH
= CH- or a single bond; each atom constituting these compounds may be substituted with its isotope. A) a liquid crystal composition comprising at least one compound selected from the group consisting of: 13. A compound comprising at least one compound according to claim 1 as a first component,
As the second component, at least one compound selected from the compound group consisting of the general formulas (5) and (6) is contained, and as the third component, the general formulas (7), (8) and (9) are included. A liquid crystal composition comprising at least one compound selected from the group consisting of: 14. A compound comprising at least one compound according to claim 1 as a first component,
As a part of the second component, at least one compound selected from the compound group consisting of the general formulas (2), (3), and (4) is contained, and as another part of the second component, the general formula (5) ) And at least one compound selected from the compound group consisting of (6), and as a third component, at least a compound selected from the compound group consisting of general formulas (7), (8) and (9) A liquid crystal composition comprising one type. 15. A liquid crystal composition according to claim 9, further comprising one or more optically active compounds. 16. A liquid crystal display device comprising the liquid crystal composition according to claim 9. Description: